Chlorination of meta styrene



v composition has excellent compositions. I

I have discovered that the incorporation Patented Dec. 13, 1932 UNITED STATES PAT NT" OFFICE HARRY n. mzxsrBA, or wmmeromnsrawsns, ASSIGNOR no n. 1.1m rolrr nn NEMoURs a comrm, or WILMINGTON, DELAWARE, A CORPORATION or IDELA-' WARE R o Drawing.

This invention. relates to new compositionsof matter. More specifically it relates to synthetic resins. Still more particularly it relates to the production of such resins by the chlorination of meta styrene, and to theiruse 8f$laSfiCS and in coating compositions.

' n object of this invention is the preparation of new compositions of matter. Another object of this invention is the preparation of new compositions ofmatter, having superior physical and chemical properties, from meta styrene. Another object is the formation of coating and plastic compositions these compositions of matter. A still further ob 'ect is the chlorination of meta styrene. ther objects will become apparent as the descri tion proceeds.

These 0 jects are accomplished, generally speaking, by chlorinating meta styrene in a suitable solvent under conditions which. favo'r nuclear substitution, of light, low temperature, and the presence of a halogen carrier.

Meta styrene, otherwise known as polymerized vinyl benzene, is a resinous substance use ful as a constituent of plastic and coating of halogen in the meta styrene complex: is particularly desirable because the resulting line, less thermoplasticity than meta styrene, excellent retention of flexibility on a 'ng, excellent adhesion, and. excellent durability.

In order to obtain a stable, chlorinated product from metastyren'e, I introduce the side chain because I find that the resin with a halogen atom substituted in the nucleus or ring is much less reactive than the resin with a halogen atom substituted in a side chain.

he presence of a reactive halogen in a resin renders it unsuitable for most purposes. r

7 Since the chlorination of meta styrene in the solid or molten state is attended with containing namely the absence tion mixture by resistance to gasoalcohol. In place. of ,arinated meta styrene solvent such as alcohol, it may also be obtained monnurxon or man s'rrnmm Application filed January 28, 1980. Serial No. 424,188.

difliculties,

being too reactive to use for this became necessary to find suitable rachloroethylene, tetrachloroethane, and carbon tetrachloride are solvents for meta styrene which serve the purpose, but I prefer purpose, it

to use carbon tetrachloride because of its halogen carriers favor nuclear halogen substitution. The chlorine is introduced into a carbon tetrachloride solution of meta styrene, preferably with stirring, at such a rate that absorption of chlorine is complete. the desired amount of chlorine has been introduced, as measured by a flowmeter, the reacdark place until all'the chlorine has reacted. The product is then separated from the reaca process consistingin filtering toremove any solid catalyst, washing with dilute alkali to remove hydrogen chlo- Q ride and dissolved catalyst, and precipitating the product as a white powder by pouring into precipitating the chloby pouring it into a nonas a resinous mass by removing the carbon tetrachloride by distillation, preferably un'- chlorine into the nucleus rather than in the der reduced pressure. 'I find that the products thus obtained 'are soluble in aromatic hydrocarbons and in the ordinary ester solvents.

The process for the chlorination of meta styrene described above is applicable to all in the a sence of a cataylst, renders them I carry out the reaction in a suitable solution. The common lacquer solvents and the presence of When "tion mixture is allowed to remain in a cold, 5

ot a catalyst,

" tion in which suitable for use in spraying compositions.

Emampla ll mixture of 360 meta styrene prepared by heating a solution of styrene in the absence E2200 carbon tetrachloride, about 10 g. water, and 10 iron filings was treated with chlorine at 0-l G. at a rate of about M g. per minute for three hours. The reaction mixture was kept in a cold, dark room for twenty-tour hours and was then filtered. The filtrate was washed first with dilute sodium hydroxide solution until all the hydrogen chloride and iron chloride were removed, and then with water. lhe greater portion of the carbon tetrachloride was removed by distillation under reduced pressure. The residue was poured into alcocent solutions of the product could be sprayed 1101 which caused the chlorinated meta styrene to separate as a white powder.

.E'wcmple H A mixture of 156 ot' meta styrene of the same type as that used in Example l, 1500 g. carbon tetrachloride, and five grams iron fil 1ngs was treated with chlorine in the dark at 16 C. until an increase in weight of 120 g. was obtained. The chlorinated product, isolatedas in Example I, weighed 233 grand contained 34.3% chlorine. Twenty-five per satisfactorily, whereas, due to cobwebbing, solutlons of the original meta styrene could not be sprayed satisfactorily even in 15% concentration.

ence of benzoyl peroxide) in 500 g. carbon Example H A solution of 52 g. meta styrene (prepared by heating a solution of styrene in the prestetrachloride containing 0.5 g. aluminum ClIIOPIdG was treated with chlorine in the dark 9.1320-25 C. until an increase in weight 60. 1s olated as in the preceding examples. Analchlorine.

of 17 g. was obtained. The product was ysis showed that the product contained 26.8%-

p EwampZaIV v A typical spraying enamel preparedfrom ing properties.

I in the dark of a solution containing ncome the chlorinated product of "Example ll had the following composition:

llhis enamel had a viscosity of about (ll poise at 25 C. and had satisfactory spray- The films became tack-tree within 56 minutes and were hard within 1% minutes. The films were much less thermo' plastic, more resistant to gasoline, and about three times as durable as those oi a meta sty rene enamel having the same percentage com. position. T hey were also superior to lilms o l polymerized chlorostyrene in these respects.

All advantage of this invention is that meta styrene is converted. into a more usetul prod uct. Another advantage is that the undesir able properties possessed by meta styrene, which rendered its use in a plastic or coat ing composition diflicult, are overcome.

of matter is formed. it still turther advantage is that these resins ing point than the styrene from which they are prepared and that they are consequently less thermoplastic. A further advantage is that films of coating compositions which contain the product of my invention are harder, tougher, more durable and more resistant to gasoline than those of meta styrene.

As many apparently widely diderent embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that I do not limit myself to the specific embodiments thereof except as defined in the appended claims.

I claim:

-1. Chlorinated meta styrene.

2. The product derived from'the treatment of meta styrene with chlorine under condi tions which favor nuclear substitution.

3. The product derived from the meta styrene with chlorine in the presence of a halogen carrier.

4. The product derived'from the treatment in the dark, at a low temperature, of a carbon tetrachloride solution of meta styrene with chlorine in the presence of water and iron filings. V

5. The method of chlorinating meta styrene consisting}: in treating a solution of meta have a higher melttoo i lllll styrene with chlorine under conditions which favor nuclear substitution.

6. The iinethod of chlorinating meta styrene cons sting n treating a solutionof meta styrene in the dark with chlorine in the presence of a halogen carrier.

7. The method of chlorinating meta styrene consisting in treating a solution of meta styrene in carbon tetrachloride in the dark at a low temperature with chlorine in the presence of water and iron filings.

8. The method of preparing chlorinated metastyrene consistingin treating a solution of meta styrene in carbon tetrachloride in the dark at a low temperature, with chlorine in the presence of water and .iron filings, washing with sodium hydroxide, wa hing with water, distilling ofl carbon tetrachloride, and precipitating the chlorinated meta styrene by treatment with alcohol.

In testimony whereof, I aflix my signature.

HARRY B. DYKSTRA. 

